JPS6049463B2 - How to recover xanthine stimulants from cocoa ingredients - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering xanthine stimulants from an aqueous medium.

It is known to produce soluble cocoa by extracting cocoa components with water.

During the extraction process, methyl-substituted xanthines such as theobromine and caffein are extracted along with other water-soluble solid components. However, when producing soluble cocoa, it is often desirable to have the substantial absence of these stimulants (referred to herein as xanthine stimulants). These can be removed from the extract by adsorption onto a solid adsorbent, after which the extract is essentially free of xanthine stimulants and returned to the cocoa component. Various solid adsorbents have been proposed, such as polymeric resins and activated carbon, but these can degrade the color of the cocoa component. For example, when activated carbon is used, contact between the aqueous extract and the activated carbon often leads to an increase in pH, which is said to worsen the color tone of the cocoa component. The inventor has discovered that when the adsorbent used is dispersed in water, substantially
If the reaction is neutral, undesirable color deterioration will occur.
I found that I could do it with considerably less.

According to the present invention, a method for recovering a xanthine stimulant from an aqueous solution containing the xanthine stimulant extracted from a cocoa component is provided.

The method consists of contacting the solution with a substantially neutral adsorbent and separating the adsorbent adsorbed with xanthine stimulant from an aqueous liquid with reduced xanthine stimulant content.
The 1 substance 5 upper neutrality used to describe this adsorbent is:
This means that the pH value does not substantially change when the adsorbent is immersed in water. An example of a resin adsorbent having this property is semi-baked resin XE-340 manufactured by ROhm & Haas. However, it is preferable to use activated carbon that has this property. This activated carbon can be obtained by acid-pickling carbon activated by heat and then washing with water to neutralize it, or by neutralizing acid-activated carbon with aqueous alkali and then washing with water to neutralize it. . As used herein, a content reduced by 1 is meant to include a content of zero. Aqueous solutions containing xanthine stimulants can be extracted from cocoa components by conventional methods.

The method includes adding a cocoa component to an aqueous solution of either water (preferably deionized water), an aqueous solution of cocoa 4 solids containing no xanthine 7 stimulant, or an aqueous solution of cocoa solids containing a small amount of xanthine 7 stimulant. This includes contacting the medium for a sufficient period of time to reduce the xanthine stimulant content in the cocoa component to a desired level. The cocoa component can be a cocoa mass, such as raw cocoa beans, roasted cocoa beans or roasted cocoa nibs, but the cocoa beans are washed, crushed and sieved to remove dirt, bacteria and most shell components. Preferably, it is raw, ground, unroasted cocoa nibs obtained by removal and then grinding. Extraction can be performed batchwise or in a continuous countercurrent extraction system with multiple columns. The ratio of water to cocoa components during extraction is not critical and is generally determined based on practical considerations required during industrial production.

Excess water should be avoided; such water/cocoa ratios are not suitable for extracting xanthine stimulants. Water vs.
The weight ratio of the cocoa component is 5 to 2(1) parts (preferably 10
~1(4) parts) yields satisfactory results. In a batch extraction method, a fixed weight of the cocoa component is contacted with a fixed volume of water as a fixed bed in a column or an extractor such as a suitable tumbler.

After removing the xanthine stimulant by continuously circulating the water, the water containing the xanthine stimulant is collected from the column or extractor and brought into contact with a neutral adsorbent contained in another column, and then the cocoa components are removed. Return to The total contact time depends, among other things, on the water to cocoa ratio, temperature and required removal rate of xanthine stimulant, but typically ranges from 1 hour to 1 (conversion).
for a period of time, preferably 2 to 3 hours. The temperature is, for example, 40°C to 100°C, preferably 70°C to 9°C under atmospheric pressure.
A temperature of 5° C. is sufficient, and if extraction is carried out under pressure, it will be higher. In continuous countercurrent extraction, water flows through a multi-cell extraction system containing cocoa components.

Water enters the extraction system first in the cell containing the most depleted batch of cocoa ingredients, passes successively through the batches of fresh cocoa ingredients contained in the cells, and finally exits the cell containing the freshest batch of cocoa ingredients. The temperature of the water when it enters the cell containing the most depleted cocoa component is between 40°C and 1°C under atmospheric pressure.
The temperature may be 00°C, preferably 70°C to 95°C, and even higher if the extraction is carried out under pressure. By choosing the cell number and circulation time, obtain the desired extraction of the xanthine stimulant. Using up to 8 consecutive cells, the circulation time can be made from 1 to 12 alpha cycles. The aqueous extract containing the xanthine stimulant and other solids is concentrated and then
The xanthine stimulant can be removed by contact with a neutral adsorbent, for example in a countercurrent system.

In such systems, the adsorbent is contained in several columns and the extract flows through these successive columns. Regular! Initially, remove the most saturated column from the system and add a column containing fresh sorbent. The temperature in the column is conveniently 40°C or higher, preferably 70°C to 9°C.
It is 5°C. By selecting the number of columns, the circulation time of each column, and the residence time of the extract, the desired xanthine stimulant removal rate can be achieved and the amount of adsorbent used can be minimized. The weight of the adsorbent is usually 10% of the weight of the cocoa component from which the xanthine stimulant is extracted.
~20%. If necessary, the xanthine stimulant content in the aqueous solution can be reduced to virtually zero by this method. During the contact of the aqueous extract with the neutral adsorbent, in addition to the xanthine stimulant, some of the other solids are also adsorbed.

A portion of these adsorbed solids (e.g. 70% to 8%
0%) can be recovered without desorption of the xanthine stimulant by washing the adsorbent with water, for example.
Whether the sorbent is used in a batch system or a countercurrent continuous system, double the sorbent beds so that one or more can be replaced while one is flowing, and ready for continuous operation. This is desirable.

After removal of the xanthine stimulant has been completed, it is usually desirable to remix other solids present in the aqueous extract with the reduced xanthine stimulant content cocoa component to prevent excessive losses.

Various techniques are used. For example, 100% cocoa
It is pre-dried at a temperature below 'C (preferably from 60°C to 70°C) to a moisture content of preferably from 2% to 7.5% and combined directly with the extract. Alternatively, the extract is preconcentrated, for example by evaporation, to a solids content of 5% to 25% before contacting with the cocoa component. Preferably, both the cocoa component and the extract are treated in this way. That is, the cocoa component is pre-dried and the extract is pre-concentrated and then re-blended. Satisfactory remixing of the solids content is obtained after at least 2 hours (preferably after 5 to 8 hours) and at a temperature of at least 400C (
Preferably at 60°C to 80°C.

The total amount of water present is such that the final moisture content of the cocoa component is 30
% to 60% (preferably 50% to 55%). The cocoa component containing the remixed solids is then dried to a moisture content of 2% to 5% by weight and then roasted.

Roasted raw materials can be commonly used in the production of cocoa beverages or chocolate. According to a variant, the amount of solids other than the xanthine stimulant that is contacted with the cocoa component may be less than the amount extracted together with the xanthine stimulant.

Periodically, the adsorbent can be regenerated, usually by heating or solvent extraction. If necessary, the xanthine stimulant is removed from an adsorbent, for example using an aliphatic alcohol such as ethanol or a chlorinated hydrocarbon such as methylene dichloride.
It can be recovered by solvent extraction. The following examples illustrate the invention.

Parts and percentages are stated by weight, unless otherwise stated. Example 1 Neutralized activated carbon was prepared by washing commercially available thermally activated carbon with 2% hydrochloric acid and using deionized water (PH = 6) until the pH of the washing liquid was 6.
．． It was manufactured by washing with water until it reached a constant temperature of 0.

1 (1) part of raw, ground, unroasted cocoa nibs at 80°C.
In the column, contact was made with 1,10(2) water.

The light brown water containing the xanthine stimulant was continuously drained from the column and the xanthine stimulant was removed by contact with neutral activated carbon contained in another column before being refluxed to the cocoa nibs. After 2 hours, the brown aqueous extract was concentrated to 9(2) by evaporation.

The depleted cocoa nibs were dried at 65 °C for 18 hours to reduce the moisture content to 5%. The concentrated aqueous extract and dried cocoa nibs were placed in a mixer and remixed at 707° C. for 6 hours to obtain a cocoa component with a water content of 53%. The cocoa component in which all the soluble components were remixed was dried at 70° C. for one full hour and then roasted. Theopromine content in cocoa decreased from 1.30% to 0.04%, a reduction rate of 9
It was 7%. However, there was only a slight difference in the color of the extract containing substantially no xanthine stimulant compared to the extract containing the xanthine stimulant.
The color of the extract, in which the xanthine stimulant was removed by contact with unwashed carbon, was gray-black. Examples 2-6 The contact time, temperature, water:cocoa ratio, loss of solid components other than the xangan stimulant, and the amount of theopromination (DTB) achieved were as described in Example 1 as per the table below. A similar method was carried out.

Example 7 A method similar to Example 3 was carried out, allowing water to flow from the bottom of the column containing the cocoa nibs to the top.

The loss of solid components was 10.5%, while the detheopromine conversion rate was 90.4%. Example 8 Cocoa beans were washed, crushed, sieved to remove most of the dirt, bacteria and shell components, and ground to obtain raw, ground unroasted cocoa nibs.

The xanthine stimulants were continuously extracted from these raw, ground, unroasted cocoa nibs by countercurrent extraction with an aqueous solution. Four consecutive extractors were used, each containing two taps of cocoa nibs. For extraction, deionized water was used, with a temperature of 80'C entering the most depleted extractor. Xanthine stimulants and others. A light brown aqueous solution containing . The circulation time was 3 times.
The last extractor containing cocoa was removed from the system after extracting the xanthine stimulant and one containing fresh, raw, ground unroasted cocoa nibs was added every hour. The water/cocoa nibs ratio was 10:1, and the system water flow rate was 2.0 per hour.
The aqueous solution removed contained 1% dissolved solids. The extract from the least depleted cocoa was passed through two consecutive columns in a counter-current flow.

The columns each contained (a) parts of neutralized activated carbon prepared as described in Example 1. The temperature in the column was maintained at 80°C. Every 4 hours, the most saturated column was removed and a new one added.

The saturated carbon column was washed with 2.0 (4) parts per hour of running water, and the removed brown aqueous solution contained 0.7% dissolved solids in addition to the xanthine stimulant. Cocoa nibs from which the xanthine stimulant was extracted were dried to a moisture content of 5%, containing dissolved solids other than the xanthine stimulant, and concentrated in advance to a solid content of 7% by evaporation to remove the xanthine stimulant. and mixed with the corresponding extract.

Thereafter, the cocoa nibs with a moisture content of 50% were dried to give a moisture content of 5%. The detheopromine conversion rate was 97%. Example 9 Light brown water containing xanthine stimulants was
The procedure as described in Example 1 was followed except that the xanthine stimulant was removed by contacting with semi-baked resin XE-340 from &Haas.

The color of the extract containing virtually no xanthine stimulant was also light brown, and no difference was observed from water containing the xanthine stimulant. Example 10 The same method as described in Example 1 was followed, but the theopromine content of the cocoa nibs used was 1.30% instead of 1.
．． What was 399% decreased to 0.042%, and the reduction rate was 97%.

Claims (1)

[Claims] 1. A method for recovering a xanthine stimulant from an aqueous solution containing a xanthine stimulant extracted from a cocoa component, in which the solution is brought into contact with a substantially neutral adsorbent to adsorb the xanthine stimulant. The above-mentioned recovery method is characterized in that the agent is separated from an aqueous solution having a reduced xanthine content. 2. Characterized by the fact that the cocoa component is raw, ground, unroasted cocoa nibs formed by washing, crushing, sieving and grinding cocoa beans after removing most of the dirt, bacteria and shell components. The method according to claim 1, wherein: 3. Process according to claim 1 or 2, characterized in that the contacting is carried out at a temperature between 70°C and 95°C. 4. The content of the xanthine stimulant in the aqueous solution is reduced to substantially zero, and the other solids in the solution are combined with the reduced cocoa component and other water-soluble solid components of the xanthine stimulant. The method according to any one of claims 1 to 4, wherein: 5. Contact the cocoa component with an aqueous medium, recover the aqueous medium containing the xanthine stimulant liberated from the cocoa component, remove the xanthine stimulant from this medium by contact with a substantially neutral adsorbent, and remove the xanthine stimulant from the medium by contacting with a substantially neutral adsorbent. separating the stimulant-adsorbed adsorbent from an aqueous medium with a reduced xanthine stimulant content and other solids present in the aqueous medium with a reduced xanthine stimulant content; 1. A method for removing xanthine stimulants from cocoa components, characterized in that they are combined with cocoa components having a reduced content. 6. Process according to claim 5, characterized in that the xanthine stimulant content in the aqueous medium is reduced to substantially zero. 7. The method according to claim 5 or 6, characterized in that the adsorbent is substantially neutral activated carbon.